CA1316319C - Rubber hose - Google Patents
Rubber hoseInfo
- Publication number
- CA1316319C CA1316319C CA000585832A CA585832A CA1316319C CA 1316319 C CA1316319 C CA 1316319C CA 000585832 A CA000585832 A CA 000585832A CA 585832 A CA585832 A CA 585832A CA 1316319 C CA1316319 C CA 1316319C
- Authority
- CA
- Canada
- Prior art keywords
- rubber
- polymer blend
- monomer
- weight
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M37/00—Apparatus or systems for feeding liquid fuel from storage containers to carburettors or fuel-injection apparatus; Arrangements for purifying liquid fuel specially adapted for, or arranged on, internal-combustion engines
- F02M37/0011—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor
- F02M37/0017—Constructional details; Manufacturing or assembly of elements of fuel systems; Materials therefor related to fuel pipes or their connections, e.g. joints or sealings
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
- F16L11/085—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more braided layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S138/00—Pipes and tubular conduits
- Y10S138/03—Polytetrafluoroethylene, i.e. PTFE
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
ABSTRACT OF DISCLOSURE
A rubber hose having an outer rubber tube and an inner rubber tube located radially inwardly of the outer rubber tube, the inner rubber tube including an inner layer and an outer layer located between the inner layer and the outer rubber tube, the inner layer being formed of a first polymer blend of acrylic rubber and fluorine-contained resin, the outer layer being formed of a second polymer blend which is different from the first polymer blend and which contains epichlorohydrin rubber. The rubber hose may further have a reinforcing fiber layer disposed between the outer rubber tube and the outer layer of the inner rubber tube such that the inner and outer rubber tubes and the fiber layer constitute an integral tubular body.
A rubber hose having an outer rubber tube and an inner rubber tube located radially inwardly of the outer rubber tube, the inner rubber tube including an inner layer and an outer layer located between the inner layer and the outer rubber tube, the inner layer being formed of a first polymer blend of acrylic rubber and fluorine-contained resin, the outer layer being formed of a second polymer blend which is different from the first polymer blend and which contains epichlorohydrin rubber. The rubber hose may further have a reinforcing fiber layer disposed between the outer rubber tube and the outer layer of the inner rubber tube such that the inner and outer rubber tubes and the fiber layer constitute an integral tubular body.
Description
- 1 131~3~
TITL~ OF T~ VE~TIO~
RUBBER HOS~
BAC~GROUND OF T~g I~V~TIO~
Field of the Invention The present invention relates generally to a rubber hose and particularly to such a rubber hose suitable as a fuel line in an automotive engine compartment where the hose connects metal lines.
Discussion_of Prior Art A conventional rubber hose used as an automotive fuel line has a laminated-tube structure consisting of an iDner rubber ~ube having gasoline resis~ance (or resistance to gasoline), a reinforcing flber layer and an outer rubber tube having weather resistance. The opposite ends of the rubber hose are fitted onto respective metal pipes and the fitted ends of the rubber hose are tightly fastened to the metal pipes.
As a result of recent developments in automobile technology, automotive fuel such as gasoline i~ sub~ected to high pressure and high temperature for the purpose of regulating exhaust gas.
Additionally, the automotive engine compartment i8 sub~ected to extremely wide ~emperature variations from lower than -40C to higher than 100C. Gasoline transported through the high temperature engine compartment tend~ to be oxidized due to the heat. Gasoline containing peroxides whlch are developed due to such heat, i8 called "sour gasoline", The sour gasoline adversely influences the rubber hoses transporting the fuel. Thus, nowadays, rubber hoses for automotive fuel lines are required to have superior properties, so that the hoses can be used in a qatiqfactory manner under ~e~ere condition~. The conventional rubber hoses of the type described above, which have an inner rubber tube formed of a widely u~ed polymer reqistant to gasoline, cannot be u~ed any longer in automotiqe vehicles.
Furthermore, gasoline or oil is a limited resource, which iq expected to be exhau~ted in the future. For countering such situation, alcohol may be used as an automotive fuel in admixture with gasoline. However, alcohol is corrosive to rubber. Accordingly, there will eventually arise the need for rubber hoses having an inner rubber tube resistant to alcohol.
i . . .
13~319 In view of the foregoing, it has been propose~d that the lnner rubber tube of the rubber hose be formed of fluorine-containing rubber (hereinafter referred to as ~FKM~ because ~KM has excellent heat resistance and sour-gasoline resistance. ~owever, FKM suffers from problems of low temperature resistance and high co~t of manufacture.
Against thi~ b~ckground, another type of rubber hose i~ available at present, which has a double-layered inner rubber tube consisting of a comparatively thin inner layer formed of the above-mentioned FKM and an outer layer formed of a material having excellent low temperature resistance, such as hydrin rubber or acrylonitrile-butadiene rubber (~BR) ~specifically9 ~BR which contains a comparatively small proportion of acrylonitrile and accordingly i~ excellent in low temperature resistance). ~owever, this rubber hose has the problem of hi~h co~t of manufacture, and other problems.
There ha~ also been developed a polymer blend (complex polymer) consisting of acrylic rubber and fluorine-containing resin, which has excellent sour-gaqoline resistance comparable to that of FKM but which costs le3~ than FKM. Since it contains a resin, however, the polymer blend exhibit~ a comparatively high hardness after being cured. In the case where the polymer blend i9 used for forming an inner layer of an inner rubber tube of a rubber hose, the produced hose has the problem of low ela~ticity. Furthermore, the lDner layer for~ed of the poly~er blend in question i3 not bonded with ~ufficient bonding strength to an NB~-based ou~er layer of the inner rubber tube, since the polymer blend i~ not vulcanized with hi8h bondin8 stren8th to NBR. Japanese Patent Application laid-open under Publication ~umber 62(1987)-278395 proposed to add epoxy resin, sil~oa or magnesium oxide to ~BR for ~mproving the bonding strength by Yulcanization at the interface between the inner and outer layers of the lnner rubber tube. ~owever, even the thus-produced rubber hoses have a tendency to be peeled at the interface in que~tion durlng use.
SUMMARY OF T~ IXVERTIO~
It i9 therefore an ob~ect of the pre~ent in~ention to provide a rubber hose which i~ manufactured at low cost and meet~ all the requirements for use in automotive fuel lines.
The above ob~ect has been achieved according to the princlple of .~
., :
, '~
- 3 - ~ 3 ~
the present inv~ntion, which provides a rubber hose having an outer rubber tube and an inner rubber tube located rad$ally inwardly of the outer rubber tube, the inner rubber tube compri3ing an inner layer and an outer layer located between the in~er layer and the outer rubber tube, the inner layer being formed of a fir~t polymer blend of acrylic rubber and fluorine-containing resin~ the outer layer being formed of a second polymer blend different from the first polymer blend, the second polymer blend containing epichlorohydrin rubber.
~he inventors have conducted a serieQ of studies for developing the art of preventing peeling or separation at the interface between the inner and outer layers of the inner rubber tube of a rubber hose, the inner layer being formed of a polymer blend of acrylic rubber and fluorine-containing resin, the outer layer being formed of a polymer blend containing NBR, for example. The present i~ention i8 based on those ~tudies. The ln~entor~ have found that, if the outer layer of the inner rubber tube i9 formed of a poly~er blend (b) which ls different from a polymer blend ~a) used for formiDg the inner layer and which contAins epichlorohydrin rubber, the iDner and outer layer~
are vulcanized to each other with high bonding or adhe-~lve strength and, additionally, deterioration of the low temperature characteristic of the inner layer i~ prevented.
The rubber hose of the present in~ention a~ de3cribed above ha~
excellent characteristics, particularly regarding gasoline resiseance, sour-gssoline re~istance and heat resi~tance, ~nd additionally the cost of manufacture ~hereof ie comparatively low. Moreover9 the inner and outer layers of the inner rubber tube of the hose are ~ulcanlzed to each other with sufficient bonding strength. Thus, the rubber hose of the present invention can be used even under severe conditionq, and is particularly suitable for use in an automotive fuel line w~ere the hoses used therei~ are required to maintain a high seal characteristic for a comparatively long period of time.
In a preferred embodiment of the prese~t invention, the rubber hose further has a relnforcing fiber lsyer disposed between the outer rubber tube and the outer layer of the inner rubber tube such that the inner and outer rubber tubes and the reinforcing fiber layer constitute an integral tubular body.
. ~
~31~31.9 In one embodiment of ~he invention, the ~econd polymer blend contains epichlorohydrin rubber and at least one polymer selected from the group consisting of acrylonitrile-butadiene rubber, chlorosulfonated polye~hylene, chlorlnated polyethylene and acrylic rubber.
In another embodiment of the invention, the second polymer blend contain~ 1-50 partA by weight of epichlorohydri~ rubber p r 100 parts by weight of the ~econd polymer blend.
In yet another embodiment of the invention, the second polymer blend further contain~ 15-80 part~ by we~ght of at least one plasticizer per 100 parts by weight of acrylonitrlle-butadiene rubber which contain~ 30-55% by weight of acrylonitrile.
In a still further embodlment of the i~ventlon, the acrylic rubber of the first polymer blend i8 copolymer rubber produced by copolymerization of at lea~t four monomera, the at least four monoMers including (A) at least one first monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate; ~B) at lea~t one second monomer selec~ed from the group conslsting of substltuted-alkyl ester of acrylic acid and substituted-alkyl ester of met~acrylic acld;
(C) at least one third monomer ~elected from the group consisting of diene, acrylate containing dihydrodicyclopentadienyl radical, methacrylate containing di~ydrodicyclopentadienyl radical, ethylenically unsaturated monomer containlng epoxy radical, and ethylenically unsatura~ed compound containing active halogen; and (D) at least one fourth monomer selected from a group consi~ting of other ethylenically unsaturated compounds capable of copolymerizing wi~h the above-indicated at least three monomers ~A), (B) and (C).
In another embodiment of the invention, the acrylic rubber of the first polymer blend consist3 of, as polymerization monomers thereof, 30-80% by weight of the at least one first monomer (A); 20-70% by weight of the at least one econd monomer (B); 0.1-10% by weight of the:at least one third monomer (C); and 1-30~ by weight of the at least one fourth monomer (D).
In yet another embodiment of the in~ention, the fluorine-containing resin of the first polymer blend comprises polyvinyl fluoride, polyvinylidene fluoride, .
, ' ., .
13~53~ ~
tetrafluoroethylene-hexafluoroethylene copolymer, polytetrafluoroethylene, or e~hylene-tetrafluoroethylene copolymer.
BRIEF DESCBIPTIO~ OF T~ D~WI~GS
The above and optional obJect~, feature~ and advantages of the present invention will be better understood by reading the following detailed description of the presen~ly preferred embodiment of the invention, when con~idered in conJunction with the accompanylng drawings, in ~hich~
Fig. 1 is a transverse cross sectlonal view of one embodim~nt of the rubber hose of th& present invention;
Fig. 2 is a transYerse cross ~ectional ~iew of a conventional rubber hose; and Fig. 3 is a lo~gitudinal cross sectional view of the rubber hose of Fig. 2 when used together with metallic pipes.
D~TAIL~D PXSC~IPTIO~ OF P~IOR A~T
~ eferring to Fig. 2, there is shown a conventional rubber hose 104 for an automotive fuel line. The rubber hose 104 has a laminated-tube s~ructure consisting of an inner rubber tube 101 ha~i~g gasoline resistance, a reinforcing fiber layer 102 and an outer rubber tube 103 having weather resistance. Referring further to Fig. 3, the pair of opposite ends of the rubber ho~e 104 are fitted onto respective metallic pipe~ 105 and the fitted ends of the rubber hoQe 104 are tightly fastened to the metallic pipes 105 with the help of respective fastening bands 106.
D~TAII~D D~C~IPTIO~_OF T~ P~F~K~ED EMBODIME~T
The inner laye~ of the inner rubber tube of the rubber ho3e of the ~resent inv~ntion, is formed of a poly~er blend (a) of acrylic rubber and fluorine-contained resin, ~hile the outer layer of the inner rubber tube i~ formed of a polymer blend (b) different from the polymer blend (a) and containing epichlorohydrin.
As the acrylic rubber used for prepari~8 the above-indicated polymer blend (a), preferably are used copolymer rubbers which are produced by copolymerization of multiple elements, that i8~ at lea~t four monomers including at least one monomer selected from each of the followin~ four monomer groups (A) through (D):
(A): alkyl acrylate and alkyl methacrylate;
-- 6 - 1~ 3 (B): substituted-alkyl ester of acryllc acid and substituted-alkyl ester o~ methacrylic acid;
(C): diene, acryla~e-containing dihydrodicyclopentadienyl radical and methacrylate-containing dihydrodicyclopentadienyl radical, ethylenically unsaturated compound contalning epoxy radical, and ethylenically unsaturated compotmd containing active halogen; and (D): ethylenically unsaturated compound different from the above mo~omers (A), (B) and (C) capable of copolymerizing with the monomers (A), (B) and (C).
As descr~bed above, the at least four monomers include at l~ast one monomer selected from each of the above-indicated groups (A) through (D)~
The alkyl acrylate and alkyl methacryla~e of the monomer (A) is represented by the followiDg general formula ~1):
Rl ~
~2C = C - C - OR2 ...(1) wherein Rl i8 H or CH3 radical and ~2 is alkyl radical.
Preferably, the number of carbon toms contained in the alkyl radical R2 i-~ within the raDge of 3 to 8. For example, the mo~o~ers (A) include n-butyl acrylate, n-~exyl acrylate, n-octyl acrylate and 2-ethylhexyl scrylate.
Next, the substituted-alkyl ester of acrylic acid and substituted-alkyl ester of methacrylic acid of the monomer (B) is represented by the following general formula (2):
Rl O
H2C = ~ - C - ORs .~.(2 wherein Rl is ~ or C~3 radlcal and Ra i8 substituted alkyl radical.
Preferably, the substituted alkyl radical B3 has a monovalent substituent such as alXoxy radical or cyano radical. As the alkoxy radical substituted alkyl radicals, are preferably alkyl radicals whose number of carbon atoms is withln the rang~ of 1 to 4 and which are substituted with alkoxy radicals whose number of carbon atoms is within the range of 1 to 4. Meanwhile, as the cyano radical substituted alkyl radicals, are preferably cyanoalkyl radicals whose ' . :, . ... .
;
. : :
:. :
~" . :
~ 3~ ~3~
number of carbon atom~ i~ within the range of 2 to 12.
The alkoxyalkyl esters of acrylic acid of the monomer (B~ include methoxyethyl s~rylate, methoxymethyl acrylate, etho~ye~hyl acrylate, bu~oxyethyl acrylate, methoxyethoxyethyl acrylate and ethoxyethoxyethyl acrylate.
The cyanoalkyl esters of acrylic ac~t or ~ethacrylic acid of the monomer (B) include cyanomethyl acrylate, cyanomethyl methacrylateg 1 cyanoethyl acrylate, l-cyanoethyl methacrylate, 2-cyanoethyl acrylateJ 2-cyanoethyl me~hacrylate, l-cyanopropyl acrylate, l-cyanopropyl methacrylate9 2-cyanopropyl acrylate, 2-cyanopropyl methacrylate, 3-cyanopropyl acrylate, 3-cyanopropyl methacrylate, 4-cyanobutyl acrylate, 4-cyanobu~yl methacrylate, 6-cyanohexyl acrylate, 6-cyanohexyl methacrylate, 2-ethyl-6-cyanohexyl acrylate, 2-ethyl-6-cyanohexyl methacrylate, 8-cyanooctyl acrylate and 8-cyanooctyl ~ethacrylateO Above all, 2-cyanoethyl acrylate, 3-cyanopropyl acrylate and 4-cyanobutyl acrylate are preferred.
As the diene of the monomer (C), preferably u3ed are non-con~ugated dieneQ ~uch as al~ylidene norbornene, alkenyl norbornene, dicyclopentadiene, methylcyclopentadlene and their dimers;
and con~ugated dienes such as butadiene ~nd lsoprene. Above 811, is preferred a non-con~ugated diene selected from the group consi~ting of alkylidene norbornene, alkenyl norbornene, dicyclopentadiene, methylcyclopentadiene and their dimers.
A~ the acrylate-containing dihydrodicyclopentadienyl or ~ethacrylate-containing dihydrodicyclopentadienyl radical of the monomer (C), preferably are used dihydrodicyclopentadienyl acrylate, dihydrodicyclopen~adienyl methacrylate, dihydrodicyclopentadienyloxyethyl acrylate and dihydrodicyclopentadienyloxyethyl methacrylate.
As the ethylenically un~aturated compound containing epoxy radical of the monomer (C), preferably are used allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
As the ethylenically unsaturated co~pound containing active halogen of the monomer (C), preferably are used vinyl benzyl chloride, vinyl benzyl bromide, 2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropionate, .
3 ~ ~
2-chloroe~hyl acrylate, 2-chloroethyl methacrylate, chloromethyl vinyl ketone and 2-chloroacetoxy-methyl-5-norbornene.
As the ethylenically un~aturated compound of the monomer ~D), preferably are used monomer containin8 carboxyl radical, such ns acrylic acld, methacrylic acid, crotonic acid, 2-pentenic acid, maleic acid, fumaric acid and itaconic acid; methacrylate such as methyl methacrylate a~d octyl methacrylate; alkoxyalkyl acrylate such as methoxyethyl acrylate and buto~yethyl acrylate; alkyl ~lnyl ketone such a3 methyl vinyl ketone; vinyl such as vinyl ethyl ether and allyl methyl ether; vinyl aromatic monomer such as allyl ether, styrene, a-methyl styrene, chlorostyrene and vinyl ~oluene; Yinyl nitrile such as acrylonitrile and ~ethacrylonitrile; ~inyl amide such as acrylamide, methacrylamide and ~-methylol acrylamlde; ~inyl chloride;
vinylidene chloride; and alkyl fumarate.
Preferably, the acrylic rubber of the polymer blend (a) contains~
aQ polymerization monomers thereof, 30-80X by weight of the at least one first monomer (A), 20-70% by weight of the at least one second monomer (B), O.l-lOX by weight of the at least one third monomer (C) and 1-30~ by weight of the at least one fourth ~onomer (D).
If the proportion of the monomer (A) i8 below the lower limit of the above-indicated range therefor, the inner layer formed of the polymer blend ~a) ~uffer~ from insufficient heat reslstance. On the other hand, if that proportion e~ceed~ the upper limit of the range, the normal-state characteristics of the inner layer are deterlorated.
If the proportion of the monomer (B) is lower than the lower limit of the above-indicated range therefor, the l~ner layer is insufficient in gasoline resistance and sour-gasoline resistance. On the other hand, if that proportion eYceeds the upper limit of the range, the normal-state characteristics of the inner layer are deteriorated.
If the proport~on of each of the monomers (C) and tD) exceed3 the upper limit of the above-indica~ed corresponding range therefor, the inner layer tends to lose the balance between the gasoline re~istance, sour-gasoline resistance and heat resistance thereof.
A~ the fluorine-containing re~in of the polymer blend (a), preferably are u~ed polyvinyl fluoride (PVF), polyvinylldene fluoride .
~3~3~
g (PVDF), polytetrafluoroethylene (PTF~), tetrafluoroethylene-hexafluoroethylene copolymer ~F~P) and ethylene-tetrafluoroethylene copolymer (~TF).
The polymer blend (a) i~ mi~ed with com~only used addltives, as needed, such as reinforciDB agent, filler, plasticizer, softener, cross linking agent and/or stabilizer. Also, polymer such a~
polyvinyl chloride or epichlorohydrin rubber may be added to the polymer blend (a~ as needed.
The outer layer of the inner rubber tube of the rubber ho~e of the present invention is formed of the polymer blend (b) which i~
different from the above-discussed polymer blend (a) and contains eplchlor~hydrin rubber.
As the polymer(s), other than epichlorohydrin rubber, used for preparing the polymer blend (b), preferably are used acrylonitrile-butadiene rubber (NBR3, chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE) and acrylic rubber (~CM). One or more of those polymers are used together wlth epichlorohydrin rubber to prepare the polymer blend (b).
The NB~ u~ed to prepare the polymer blend (b) i8 not specified with respect ~o an amount or percentage by weight ("A~ amount") of acrylonitrile copolymerized or contained therein. Similarly, the CSM
or CPE used in the polymer blend (b) i~ not specified with respect to an amount of chlorine contained therein.
The epichlorohydrin rubber (C~C) employed for preparing the polymer blend (b) i8 by no means limited to a specific kind, 80 long as the CHC contains eplchlorohydrin as polymerization u~it. In addit~on to epichlorohydrln contained as the essential polymeriza~ion unit, the C~C may contain as an optional polymerization unit at least one monomer selected from the group of ethylene oxide, allyl glycidyl ether, and a compound capable of copolymerizing with eplchlorohydrin, ethylene oxide and allyl glyci~yl ether.
Preferably, the polymer blend (b) contains 1-50 parts by ~eight of epichlorohydrin rubber per 100 parts by weight o~ the overall polymer blend ~b), that is, the epichlorohydrin rubber and the above-indicated ot~er polymer(s).
The polymer blend (b) is mixed, a~ needed, with one or more - 10 - ~L3~L~3~9 conventionally used pla~ticizers selected from the group consisting of a synthesized plastici~er such as dibutyl phthalate (DBP) 9 octyl phthalate (DOP) and tricresyl phosphate (TCP); and a polyol-type plasticizer such as ethylene glycol. It is recommended that 15-80 parts by weight of the plasticizer(s) be used together with 100 parts by weight of ~BR which contains 30--S5% by weight of acrylonitrile (namely9 the AN amount of the NBR is 30-35%).
In this case, bleeding of the plasticizer(s) from the inner layer into ~he outer layer due to a concentration gradient therebetween iB
prevented.
The polymer blend ~b) is mixed with oth~r materials such ag reinforcing agent, filler, softener, cross-linking agent and stabilizer, as needed.
The rubber hose has a reinforcing fiber layer formed on an outer surface of the outer layer which is formed of the specific polymer blend (b) contalning CHC, ~hich layer i8 formed on an outer surface of the inner l~yer formed of the blend polymer (a) of acrylic rubber and fluorine-contained resin, the inner and outer layer~ cooperating with each other ~o con~titute the lnner rubber tube. Th0 I~bber hose further has an outer rubber tube formed on an outer surface of the reinforclng fiber layer.
The reinforcing fiber layer is formed in a con~entional manner by braiding, spiralling or knitting9 usin8 synthetic fiber such as polyester fiber or aramid fiber, or natural fiber such as co~ton fiber.
The outer rubber tube is formed of commonly used material. From the standpoint of weather resi~tance, heat resistance and water permeability, the outer rubber tube preferably i~ formed of ethylene-propylene-diene rubber (EPDM) or CHC.
There will be de~cribed a method of manufacturing the rubber hose as described above.
First, the blend polymer (b) containing C~C is Xneaded by a cooling roller, while the blend polymer (a) o~ acrylic rubber and fluorine-contained resin i~ kneaded in the same ~anner. The kneaded blends (a) and ~b) are used to concurrently extrude an lDner and an outer layer of an inner rubber tube. Alternatively, the kneaded blends (a) and ~b) are extruded by two extruders to form an lnner !.
. .
.
11 - ~ 3~3~3 layer and sub~equently an outer layer onto the i~ner layer, respectively. ~ext, a reinforcing fiber layer is formed on an outer surface of the outer layer of the lnner rubber tube. Last, an outer rubber tube i9 e~truded onto an outer surface of the reinforcing fiber layer. The thus obtained tubular body i8 ~ubJected to vulcanization to adhere the four laminates (three layers and one tube) to each other5 whereby the integral tubular body or hose i8 producedO The vulcanization temperature i~ selected at 145 - 170C, and the vulcani~ation period ~ selected ~t 30 - 90 minute~.
The thu~ produced rubber hose is show~ in Fig. 1. In the figure, reference la de~ignates the lnner layer formed o~ the polymer blend (a) of acrylic rubber and fluorine-containing resin, while reference lb de~i&nate~ the outer layer formed of the polymer blend (b) containing epichlorohydrin rubber. The inner ~nd outer layers la, lb cooperate wlth each other to constitute the inner rubber tube 1, whereby the inner tube 1 has a double-layered structure. Reference numeral 3 designates the outer rubber tube, ~nd the relnforcing fiber layer indicated at reference numeral 2 is dispo~ed between the i~ner and outer tubes 1, 3 such that the lr~er and outer tubes 1, 3 and the fiber layer 2 constitute an integral tubular body or hose 4.
The rubber hose constructed and manufactured as described above exhibits ~cellent character~stics, particularly with respec~ to gasoline resistance, sour-gasoline re~i~ta~ce and heat resistance, and additionally lts cost is comparatively low. Moreover9 the inner and outer layers of the inner rubber tube of the rubber hose are vulcanized to each other with high bonding strength, and accordingly the rubber hose i8 free from the problem of peeliDg at the interf~ce between the iDner and outer layers of the inner rubber tube.
While the present invention has been illustrated in the presently preferred embodlment wlth particularities, lt is to be understood that the present invention may be embodied ~ith various changes~
improvements and ~odification~ tha~ may occur to those skilled in the art without departing from the spirit and scope of the invention.
Accordingly, the present invention is by no means limited to the following examples prepared for conducting a bondlng-strength comparison test.
. . . -.', ~,, ~ .
.
; ~ ., . ~
~ 3 ~
~AMPLES
E~amples 1 through 7 shown in the TAsLE are composition~ prepared according to the pre~ent invention to be used a~ material for forming the outer layer ~lb) of the inner rubber tube (1) of the rubber ho3e (4). The compositions of Invention Examples 1-7 contain respective polymer blend~ indicated in the TABLE. The TABLE also ~hows Compar~tive E~amples 1 through 5 having respective composition~
indicated thereln.
Meanwhile9 the followlng composltion was prepared for use a~
material for the inner layer ~la) of the inner rubber tube (1):
Com~03ition for Inner LaYer (parts by welght) acryllc rubber containing 35% of vinylidene fluoride resin ("~R-ll"* available from Japan 100 Synthe~ic Bubber Co., Ltd.
stearic aeid ISAF carbon 30 plasticizer ("TP-95"* available from Thiokol Chemical Corp.) 25 vulcanizing agent ("DIAK No. l"* available from ~.I. du Pont de Nemoure & Co.) Each of the composition for the inner layer and the composition~
for the outer layer (Invention Examples 1-7 and Comparative ~xamples 1-5) was formed into a rubber ~heet of a 2 mm thickne~s by an extruder. Each of the rubber sheet3 formed of Invention ~xamples 1-7 and Comparative Examples 1-5 wa~ superposed on the rubber sheet formed of the composltion for the inner layer, and the superposed rubber sheets are ~ulcanized at 160C for 60 minutes so as to produce a test piece. Subseguently, each test piece wa~ sub~ected to a 180-degree peel test wherein the pair of rubber ~heets of the piece were pulled in opposite directions (that i9, with lB0 degree~ between the ~heets).
The test results are shown in the bottom portion of the TABL~.
* Trade Mark ~ , .; ", . . .
.
. . .
`` - l3 - ~ 3 ~
~' A B L E
( parts by weiclht ) INVENTION EXAMPLES COMPARATIVE EXAMPLES
1 2 3 4 5 6 7 1 2_3 4 5 5NBR*l95 90 70 50 - - - 100 - -CHC*25 10 30 50 3030 30 - 100 - - -CSM*3 - - - - 70 - ~ - - 100 CPE*4 - - - 70 - - - - 100 10SA*5 1 1 1 1 1 - 1 ZnO 5 5 5 5 - - - 5 ~
. MgO 5 5 5 5 10 10 - 5 5 10 10 C *6 50 5050 50 50 5050 50 50 50 50 50 Pla*7 15 1515 15 15 1515 15 15 15 15 15 1S VA*8 3.3 3.33.33.3 2 3 1 3.31 2 3 S *9 0.5 0.5 0.5 0.5 - -- - 0.5 - - - -~ _ _ .
PF*x 6.0 10.1 13.2 14.0 12.6 11.0 13.7 4.4 6.8 4.0 2.7 5.3 RF/IP RF RF RF RF RF RF RF IP IP IP IP IP
*1: NBR containing 32% by weight of AN (acrylonitrile) *2: epichloxohydrin-ethylene oxide-allyl glycidyl ether copolymer *3: CSM containing 35% by weight of CQ
*4: CPE containing 35% by ~eight of CQ
25 *5 stearic acid *6: FEF carbon *7: plasticizer *8: vulcanization accelerator *9: sulfur 30 *x: Pulling Force (kg/inch) *y: fracture of the rubber sheets of test pi.ece *z: peeling at the interface between the rubber sheets of test piece :, :
:
: .
' As 15 apparen~ from the test results shown in the TAEL~, all the test pleces formed of the compositions of Invention ~xample~ 1-7 were not peeled at the interface between the pair of superposed rubber sheets thereof, but fractured in the (sheet) rubber. That is, the rubber sheets themselves were fractured. Thi~ means high bonding strength at the interface between the rubber sheets of the tes~
pieces. 0~ the other hand, the test pieces formed of the compositions of Comparative Examples 1-5 were peeled at the interface between the pair of superpo~ed rubber sheets thereof. ~hi~ means low bonding strength at the interface~ a~ contrasted with the high bondiDg strength for Inve~tion E~ample~ 1-7. Thus, it is understood ~hat the compositions prepared according to the present invention (Invention ~xamples 1-7) are superior as materials for forming the inner layer of the inner rubber tube of rubber ho~es, to comparative compositions 1-5.
.
.
: . :.
, : . ., `, ' ' ' , :, ' . ,: :-.
TITL~ OF T~ VE~TIO~
RUBBER HOS~
BAC~GROUND OF T~g I~V~TIO~
Field of the Invention The present invention relates generally to a rubber hose and particularly to such a rubber hose suitable as a fuel line in an automotive engine compartment where the hose connects metal lines.
Discussion_of Prior Art A conventional rubber hose used as an automotive fuel line has a laminated-tube structure consisting of an iDner rubber ~ube having gasoline resis~ance (or resistance to gasoline), a reinforcing flber layer and an outer rubber tube having weather resistance. The opposite ends of the rubber hose are fitted onto respective metal pipes and the fitted ends of the rubber hose are tightly fastened to the metal pipes.
As a result of recent developments in automobile technology, automotive fuel such as gasoline i~ sub~ected to high pressure and high temperature for the purpose of regulating exhaust gas.
Additionally, the automotive engine compartment i8 sub~ected to extremely wide ~emperature variations from lower than -40C to higher than 100C. Gasoline transported through the high temperature engine compartment tend~ to be oxidized due to the heat. Gasoline containing peroxides whlch are developed due to such heat, i8 called "sour gasoline", The sour gasoline adversely influences the rubber hoses transporting the fuel. Thus, nowadays, rubber hoses for automotive fuel lines are required to have superior properties, so that the hoses can be used in a qatiqfactory manner under ~e~ere condition~. The conventional rubber hoses of the type described above, which have an inner rubber tube formed of a widely u~ed polymer reqistant to gasoline, cannot be u~ed any longer in automotiqe vehicles.
Furthermore, gasoline or oil is a limited resource, which iq expected to be exhau~ted in the future. For countering such situation, alcohol may be used as an automotive fuel in admixture with gasoline. However, alcohol is corrosive to rubber. Accordingly, there will eventually arise the need for rubber hoses having an inner rubber tube resistant to alcohol.
i . . .
13~319 In view of the foregoing, it has been propose~d that the lnner rubber tube of the rubber hose be formed of fluorine-containing rubber (hereinafter referred to as ~FKM~ because ~KM has excellent heat resistance and sour-gasoline resistance. ~owever, FKM suffers from problems of low temperature resistance and high co~t of manufacture.
Against thi~ b~ckground, another type of rubber hose i~ available at present, which has a double-layered inner rubber tube consisting of a comparatively thin inner layer formed of the above-mentioned FKM and an outer layer formed of a material having excellent low temperature resistance, such as hydrin rubber or acrylonitrile-butadiene rubber (~BR) ~specifically9 ~BR which contains a comparatively small proportion of acrylonitrile and accordingly i~ excellent in low temperature resistance). ~owever, this rubber hose has the problem of hi~h co~t of manufacture, and other problems.
There ha~ also been developed a polymer blend (complex polymer) consisting of acrylic rubber and fluorine-containing resin, which has excellent sour-gaqoline resistance comparable to that of FKM but which costs le3~ than FKM. Since it contains a resin, however, the polymer blend exhibit~ a comparatively high hardness after being cured. In the case where the polymer blend i9 used for forming an inner layer of an inner rubber tube of a rubber hose, the produced hose has the problem of low ela~ticity. Furthermore, the lDner layer for~ed of the poly~er blend in question i3 not bonded with ~ufficient bonding strength to an NB~-based ou~er layer of the inner rubber tube, since the polymer blend i~ not vulcanized with hi8h bondin8 stren8th to NBR. Japanese Patent Application laid-open under Publication ~umber 62(1987)-278395 proposed to add epoxy resin, sil~oa or magnesium oxide to ~BR for ~mproving the bonding strength by Yulcanization at the interface between the inner and outer layers of the lnner rubber tube. ~owever, even the thus-produced rubber hoses have a tendency to be peeled at the interface in que~tion durlng use.
SUMMARY OF T~ IXVERTIO~
It i9 therefore an ob~ect of the pre~ent in~ention to provide a rubber hose which i~ manufactured at low cost and meet~ all the requirements for use in automotive fuel lines.
The above ob~ect has been achieved according to the princlple of .~
., :
, '~
- 3 - ~ 3 ~
the present inv~ntion, which provides a rubber hose having an outer rubber tube and an inner rubber tube located rad$ally inwardly of the outer rubber tube, the inner rubber tube compri3ing an inner layer and an outer layer located between the in~er layer and the outer rubber tube, the inner layer being formed of a fir~t polymer blend of acrylic rubber and fluorine-containing resin~ the outer layer being formed of a second polymer blend different from the first polymer blend, the second polymer blend containing epichlorohydrin rubber.
~he inventors have conducted a serieQ of studies for developing the art of preventing peeling or separation at the interface between the inner and outer layers of the inner rubber tube of a rubber hose, the inner layer being formed of a polymer blend of acrylic rubber and fluorine-containing resin, the outer layer being formed of a polymer blend containing NBR, for example. The present i~ention i8 based on those ~tudies. The ln~entor~ have found that, if the outer layer of the inner rubber tube i9 formed of a poly~er blend (b) which ls different from a polymer blend ~a) used for formiDg the inner layer and which contAins epichlorohydrin rubber, the iDner and outer layer~
are vulcanized to each other with high bonding or adhe-~lve strength and, additionally, deterioration of the low temperature characteristic of the inner layer i~ prevented.
The rubber hose of the present in~ention a~ de3cribed above ha~
excellent characteristics, particularly regarding gasoline resiseance, sour-gssoline re~istance and heat resi~tance, ~nd additionally the cost of manufacture ~hereof ie comparatively low. Moreover9 the inner and outer layers of the inner rubber tube of the hose are ~ulcanlzed to each other with sufficient bonding strength. Thus, the rubber hose of the present invention can be used even under severe conditionq, and is particularly suitable for use in an automotive fuel line w~ere the hoses used therei~ are required to maintain a high seal characteristic for a comparatively long period of time.
In a preferred embodiment of the prese~t invention, the rubber hose further has a relnforcing fiber lsyer disposed between the outer rubber tube and the outer layer of the inner rubber tube such that the inner and outer rubber tubes and the reinforcing fiber layer constitute an integral tubular body.
. ~
~31~31.9 In one embodiment of ~he invention, the ~econd polymer blend contains epichlorohydrin rubber and at least one polymer selected from the group consisting of acrylonitrile-butadiene rubber, chlorosulfonated polye~hylene, chlorlnated polyethylene and acrylic rubber.
In another embodiment of the invention, the second polymer blend contain~ 1-50 partA by weight of epichlorohydri~ rubber p r 100 parts by weight of the ~econd polymer blend.
In yet another embodiment of the invention, the second polymer blend further contain~ 15-80 part~ by we~ght of at least one plasticizer per 100 parts by weight of acrylonitrlle-butadiene rubber which contain~ 30-55% by weight of acrylonitrile.
In a still further embodlment of the i~ventlon, the acrylic rubber of the first polymer blend i8 copolymer rubber produced by copolymerization of at lea~t four monomera, the at least four monoMers including (A) at least one first monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate; ~B) at lea~t one second monomer selec~ed from the group conslsting of substltuted-alkyl ester of acrylic acid and substituted-alkyl ester of met~acrylic acld;
(C) at least one third monomer ~elected from the group consisting of diene, acrylate containing dihydrodicyclopentadienyl radical, methacrylate containing di~ydrodicyclopentadienyl radical, ethylenically unsaturated monomer containlng epoxy radical, and ethylenically unsatura~ed compound containing active halogen; and (D) at least one fourth monomer selected from a group consi~ting of other ethylenically unsaturated compounds capable of copolymerizing wi~h the above-indicated at least three monomers ~A), (B) and (C).
In another embodiment of the invention, the acrylic rubber of the first polymer blend consist3 of, as polymerization monomers thereof, 30-80% by weight of the at least one first monomer (A); 20-70% by weight of the at least one econd monomer (B); 0.1-10% by weight of the:at least one third monomer (C); and 1-30~ by weight of the at least one fourth monomer (D).
In yet another embodiment of the in~ention, the fluorine-containing resin of the first polymer blend comprises polyvinyl fluoride, polyvinylidene fluoride, .
, ' ., .
13~53~ ~
tetrafluoroethylene-hexafluoroethylene copolymer, polytetrafluoroethylene, or e~hylene-tetrafluoroethylene copolymer.
BRIEF DESCBIPTIO~ OF T~ D~WI~GS
The above and optional obJect~, feature~ and advantages of the present invention will be better understood by reading the following detailed description of the presen~ly preferred embodiment of the invention, when con~idered in conJunction with the accompanylng drawings, in ~hich~
Fig. 1 is a transverse cross sectlonal view of one embodim~nt of the rubber hose of th& present invention;
Fig. 2 is a transYerse cross ~ectional ~iew of a conventional rubber hose; and Fig. 3 is a lo~gitudinal cross sectional view of the rubber hose of Fig. 2 when used together with metallic pipes.
D~TAIL~D PXSC~IPTIO~ OF P~IOR A~T
~ eferring to Fig. 2, there is shown a conventional rubber hose 104 for an automotive fuel line. The rubber hose 104 has a laminated-tube s~ructure consisting of an inner rubber tube 101 ha~i~g gasoline resistance, a reinforcing fiber layer 102 and an outer rubber tube 103 having weather resistance. Referring further to Fig. 3, the pair of opposite ends of the rubber ho~e 104 are fitted onto respective metallic pipe~ 105 and the fitted ends of the rubber hoQe 104 are tightly fastened to the metallic pipes 105 with the help of respective fastening bands 106.
D~TAII~D D~C~IPTIO~_OF T~ P~F~K~ED EMBODIME~T
The inner laye~ of the inner rubber tube of the rubber ho3e of the ~resent inv~ntion, is formed of a poly~er blend (a) of acrylic rubber and fluorine-contained resin, ~hile the outer layer of the inner rubber tube i~ formed of a polymer blend (b) different from the polymer blend (a) and containing epichlorohydrin.
As the acrylic rubber used for prepari~8 the above-indicated polymer blend (a), preferably are used copolymer rubbers which are produced by copolymerization of multiple elements, that i8~ at lea~t four monomers including at least one monomer selected from each of the followin~ four monomer groups (A) through (D):
(A): alkyl acrylate and alkyl methacrylate;
-- 6 - 1~ 3 (B): substituted-alkyl ester of acryllc acid and substituted-alkyl ester o~ methacrylic acid;
(C): diene, acryla~e-containing dihydrodicyclopentadienyl radical and methacrylate-containing dihydrodicyclopentadienyl radical, ethylenically unsaturated compound contalning epoxy radical, and ethylenically unsaturated compotmd containing active halogen; and (D): ethylenically unsaturated compound different from the above mo~omers (A), (B) and (C) capable of copolymerizing with the monomers (A), (B) and (C).
As descr~bed above, the at least four monomers include at l~ast one monomer selected from each of the above-indicated groups (A) through (D)~
The alkyl acrylate and alkyl methacryla~e of the monomer (A) is represented by the followiDg general formula ~1):
Rl ~
~2C = C - C - OR2 ...(1) wherein Rl i8 H or CH3 radical and ~2 is alkyl radical.
Preferably, the number of carbon toms contained in the alkyl radical R2 i-~ within the raDge of 3 to 8. For example, the mo~o~ers (A) include n-butyl acrylate, n-~exyl acrylate, n-octyl acrylate and 2-ethylhexyl scrylate.
Next, the substituted-alkyl ester of acrylic acid and substituted-alkyl ester of methacrylic acid of the monomer (B) is represented by the following general formula (2):
Rl O
H2C = ~ - C - ORs .~.(2 wherein Rl is ~ or C~3 radlcal and Ra i8 substituted alkyl radical.
Preferably, the substituted alkyl radical B3 has a monovalent substituent such as alXoxy radical or cyano radical. As the alkoxy radical substituted alkyl radicals, are preferably alkyl radicals whose number of carbon atoms is withln the rang~ of 1 to 4 and which are substituted with alkoxy radicals whose number of carbon atoms is within the range of 1 to 4. Meanwhile, as the cyano radical substituted alkyl radicals, are preferably cyanoalkyl radicals whose ' . :, . ... .
;
. : :
:. :
~" . :
~ 3~ ~3~
number of carbon atom~ i~ within the range of 2 to 12.
The alkoxyalkyl esters of acrylic acid of the monomer (B~ include methoxyethyl s~rylate, methoxymethyl acrylate, etho~ye~hyl acrylate, bu~oxyethyl acrylate, methoxyethoxyethyl acrylate and ethoxyethoxyethyl acrylate.
The cyanoalkyl esters of acrylic ac~t or ~ethacrylic acid of the monomer (B) include cyanomethyl acrylate, cyanomethyl methacrylateg 1 cyanoethyl acrylate, l-cyanoethyl methacrylate, 2-cyanoethyl acrylateJ 2-cyanoethyl me~hacrylate, l-cyanopropyl acrylate, l-cyanopropyl methacrylate9 2-cyanopropyl acrylate, 2-cyanopropyl methacrylate, 3-cyanopropyl acrylate, 3-cyanopropyl methacrylate, 4-cyanobutyl acrylate, 4-cyanobu~yl methacrylate, 6-cyanohexyl acrylate, 6-cyanohexyl methacrylate, 2-ethyl-6-cyanohexyl acrylate, 2-ethyl-6-cyanohexyl methacrylate, 8-cyanooctyl acrylate and 8-cyanooctyl ~ethacrylateO Above all, 2-cyanoethyl acrylate, 3-cyanopropyl acrylate and 4-cyanobutyl acrylate are preferred.
As the diene of the monomer (C), preferably u3ed are non-con~ugated dieneQ ~uch as al~ylidene norbornene, alkenyl norbornene, dicyclopentadiene, methylcyclopentadlene and their dimers;
and con~ugated dienes such as butadiene ~nd lsoprene. Above 811, is preferred a non-con~ugated diene selected from the group consi~ting of alkylidene norbornene, alkenyl norbornene, dicyclopentadiene, methylcyclopentadiene and their dimers.
A~ the acrylate-containing dihydrodicyclopentadienyl or ~ethacrylate-containing dihydrodicyclopentadienyl radical of the monomer (C), preferably are used dihydrodicyclopentadienyl acrylate, dihydrodicyclopen~adienyl methacrylate, dihydrodicyclopentadienyloxyethyl acrylate and dihydrodicyclopentadienyloxyethyl methacrylate.
As the ethylenically un~aturated compound containing epoxy radical of the monomer (C), preferably are used allyl glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
As the ethylenically unsaturated co~pound containing active halogen of the monomer (C), preferably are used vinyl benzyl chloride, vinyl benzyl bromide, 2-chloroethyl vinyl ether, vinyl chloroacetate, vinyl chloropropionate, allyl chloroacetate, allyl chloropropionate, .
3 ~ ~
2-chloroe~hyl acrylate, 2-chloroethyl methacrylate, chloromethyl vinyl ketone and 2-chloroacetoxy-methyl-5-norbornene.
As the ethylenically un~aturated compound of the monomer ~D), preferably are used monomer containin8 carboxyl radical, such ns acrylic acld, methacrylic acid, crotonic acid, 2-pentenic acid, maleic acid, fumaric acid and itaconic acid; methacrylate such as methyl methacrylate a~d octyl methacrylate; alkoxyalkyl acrylate such as methoxyethyl acrylate and buto~yethyl acrylate; alkyl ~lnyl ketone such a3 methyl vinyl ketone; vinyl such as vinyl ethyl ether and allyl methyl ether; vinyl aromatic monomer such as allyl ether, styrene, a-methyl styrene, chlorostyrene and vinyl ~oluene; Yinyl nitrile such as acrylonitrile and ~ethacrylonitrile; ~inyl amide such as acrylamide, methacrylamide and ~-methylol acrylamlde; ~inyl chloride;
vinylidene chloride; and alkyl fumarate.
Preferably, the acrylic rubber of the polymer blend (a) contains~
aQ polymerization monomers thereof, 30-80X by weight of the at least one first monomer (A), 20-70% by weight of the at least one second monomer (B), O.l-lOX by weight of the at least one third monomer (C) and 1-30~ by weight of the at least one fourth ~onomer (D).
If the proportion of the monomer (A) i8 below the lower limit of the above-indicated range therefor, the inner layer formed of the polymer blend ~a) ~uffer~ from insufficient heat reslstance. On the other hand, if that proportion e~ceed~ the upper limit of the range, the normal-state characteristics of the inner layer are deterlorated.
If the proportion of the monomer (B) is lower than the lower limit of the above-indicated range therefor, the l~ner layer is insufficient in gasoline resistance and sour-gasoline resistance. On the other hand, if that proportion eYceeds the upper limit of the range, the normal-state characteristics of the inner layer are deteriorated.
If the proport~on of each of the monomers (C) and tD) exceed3 the upper limit of the above-indica~ed corresponding range therefor, the inner layer tends to lose the balance between the gasoline re~istance, sour-gasoline resistance and heat resistance thereof.
A~ the fluorine-containing re~in of the polymer blend (a), preferably are u~ed polyvinyl fluoride (PVF), polyvinylldene fluoride .
~3~3~
g (PVDF), polytetrafluoroethylene (PTF~), tetrafluoroethylene-hexafluoroethylene copolymer ~F~P) and ethylene-tetrafluoroethylene copolymer (~TF).
The polymer blend (a) i~ mi~ed with com~only used addltives, as needed, such as reinforciDB agent, filler, plasticizer, softener, cross linking agent and/or stabilizer. Also, polymer such a~
polyvinyl chloride or epichlorohydrin rubber may be added to the polymer blend (a~ as needed.
The outer layer of the inner rubber tube of the rubber ho~e of the present invention is formed of the polymer blend (b) which i~
different from the above-discussed polymer blend (a) and contains eplchlor~hydrin rubber.
As the polymer(s), other than epichlorohydrin rubber, used for preparing the polymer blend (b), preferably are used acrylonitrile-butadiene rubber (NBR3, chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CPE) and acrylic rubber (~CM). One or more of those polymers are used together wlth epichlorohydrin rubber to prepare the polymer blend (b).
The NB~ u~ed to prepare the polymer blend (b) i8 not specified with respect ~o an amount or percentage by weight ("A~ amount") of acrylonitrile copolymerized or contained therein. Similarly, the CSM
or CPE used in the polymer blend (b) i~ not specified with respect to an amount of chlorine contained therein.
The epichlorohydrin rubber (C~C) employed for preparing the polymer blend (b) i8 by no means limited to a specific kind, 80 long as the CHC contains eplchlorohydrin as polymerization u~it. In addit~on to epichlorohydrln contained as the essential polymeriza~ion unit, the C~C may contain as an optional polymerization unit at least one monomer selected from the group of ethylene oxide, allyl glycidyl ether, and a compound capable of copolymerizing with eplchlorohydrin, ethylene oxide and allyl glyci~yl ether.
Preferably, the polymer blend (b) contains 1-50 parts by ~eight of epichlorohydrin rubber per 100 parts by weight o~ the overall polymer blend ~b), that is, the epichlorohydrin rubber and the above-indicated ot~er polymer(s).
The polymer blend (b) is mixed, a~ needed, with one or more - 10 - ~L3~L~3~9 conventionally used pla~ticizers selected from the group consisting of a synthesized plastici~er such as dibutyl phthalate (DBP) 9 octyl phthalate (DOP) and tricresyl phosphate (TCP); and a polyol-type plasticizer such as ethylene glycol. It is recommended that 15-80 parts by weight of the plasticizer(s) be used together with 100 parts by weight of ~BR which contains 30--S5% by weight of acrylonitrile (namely9 the AN amount of the NBR is 30-35%).
In this case, bleeding of the plasticizer(s) from the inner layer into ~he outer layer due to a concentration gradient therebetween iB
prevented.
The polymer blend ~b) is mixed with oth~r materials such ag reinforcing agent, filler, softener, cross-linking agent and stabilizer, as needed.
The rubber hose has a reinforcing fiber layer formed on an outer surface of the outer layer which is formed of the specific polymer blend (b) contalning CHC, ~hich layer i8 formed on an outer surface of the inner l~yer formed of the blend polymer (a) of acrylic rubber and fluorine-contained resin, the inner and outer layer~ cooperating with each other ~o con~titute the lnner rubber tube. Th0 I~bber hose further has an outer rubber tube formed on an outer surface of the reinforclng fiber layer.
The reinforcing fiber layer is formed in a con~entional manner by braiding, spiralling or knitting9 usin8 synthetic fiber such as polyester fiber or aramid fiber, or natural fiber such as co~ton fiber.
The outer rubber tube is formed of commonly used material. From the standpoint of weather resi~tance, heat resistance and water permeability, the outer rubber tube preferably i~ formed of ethylene-propylene-diene rubber (EPDM) or CHC.
There will be de~cribed a method of manufacturing the rubber hose as described above.
First, the blend polymer (b) containing C~C is Xneaded by a cooling roller, while the blend polymer (a) o~ acrylic rubber and fluorine-contained resin i~ kneaded in the same ~anner. The kneaded blends (a) and ~b) are used to concurrently extrude an lDner and an outer layer of an inner rubber tube. Alternatively, the kneaded blends (a) and ~b) are extruded by two extruders to form an lnner !.
. .
.
11 - ~ 3~3~3 layer and sub~equently an outer layer onto the i~ner layer, respectively. ~ext, a reinforcing fiber layer is formed on an outer surface of the outer layer of the lnner rubber tube. Last, an outer rubber tube i9 e~truded onto an outer surface of the reinforcing fiber layer. The thus obtained tubular body i8 ~ubJected to vulcanization to adhere the four laminates (three layers and one tube) to each other5 whereby the integral tubular body or hose i8 producedO The vulcanization temperature i~ selected at 145 - 170C, and the vulcani~ation period ~ selected ~t 30 - 90 minute~.
The thu~ produced rubber hose is show~ in Fig. 1. In the figure, reference la de~ignates the lnner layer formed o~ the polymer blend (a) of acrylic rubber and fluorine-containing resin, while reference lb de~i&nate~ the outer layer formed of the polymer blend (b) containing epichlorohydrin rubber. The inner ~nd outer layers la, lb cooperate wlth each other to constitute the inner rubber tube 1, whereby the inner tube 1 has a double-layered structure. Reference numeral 3 designates the outer rubber tube, ~nd the relnforcing fiber layer indicated at reference numeral 2 is dispo~ed between the i~ner and outer tubes 1, 3 such that the lr~er and outer tubes 1, 3 and the fiber layer 2 constitute an integral tubular body or hose 4.
The rubber hose constructed and manufactured as described above exhibits ~cellent character~stics, particularly with respec~ to gasoline resistance, sour-gasoline re~i~ta~ce and heat resistance, and additionally lts cost is comparatively low. Moreover9 the inner and outer layers of the inner rubber tube of the rubber hose are vulcanized to each other with high bonding strength, and accordingly the rubber hose i8 free from the problem of peeliDg at the interf~ce between the iDner and outer layers of the inner rubber tube.
While the present invention has been illustrated in the presently preferred embodlment wlth particularities, lt is to be understood that the present invention may be embodied ~ith various changes~
improvements and ~odification~ tha~ may occur to those skilled in the art without departing from the spirit and scope of the invention.
Accordingly, the present invention is by no means limited to the following examples prepared for conducting a bondlng-strength comparison test.
. . . -.', ~,, ~ .
.
; ~ ., . ~
~ 3 ~
~AMPLES
E~amples 1 through 7 shown in the TAsLE are composition~ prepared according to the pre~ent invention to be used a~ material for forming the outer layer ~lb) of the inner rubber tube (1) of the rubber ho3e (4). The compositions of Invention Examples 1-7 contain respective polymer blend~ indicated in the TABLE. The TABLE also ~hows Compar~tive E~amples 1 through 5 having respective composition~
indicated thereln.
Meanwhile9 the followlng composltion was prepared for use a~
material for the inner layer ~la) of the inner rubber tube (1):
Com~03ition for Inner LaYer (parts by welght) acryllc rubber containing 35% of vinylidene fluoride resin ("~R-ll"* available from Japan 100 Synthe~ic Bubber Co., Ltd.
stearic aeid ISAF carbon 30 plasticizer ("TP-95"* available from Thiokol Chemical Corp.) 25 vulcanizing agent ("DIAK No. l"* available from ~.I. du Pont de Nemoure & Co.) Each of the composition for the inner layer and the composition~
for the outer layer (Invention Examples 1-7 and Comparative ~xamples 1-5) was formed into a rubber ~heet of a 2 mm thickne~s by an extruder. Each of the rubber sheet3 formed of Invention ~xamples 1-7 and Comparative Examples 1-5 wa~ superposed on the rubber sheet formed of the composltion for the inner layer, and the superposed rubber sheets are ~ulcanized at 160C for 60 minutes so as to produce a test piece. Subseguently, each test piece wa~ sub~ected to a 180-degree peel test wherein the pair of rubber ~heets of the piece were pulled in opposite directions (that i9, with lB0 degree~ between the ~heets).
The test results are shown in the bottom portion of the TABL~.
* Trade Mark ~ , .; ", . . .
.
. . .
`` - l3 - ~ 3 ~
~' A B L E
( parts by weiclht ) INVENTION EXAMPLES COMPARATIVE EXAMPLES
1 2 3 4 5 6 7 1 2_3 4 5 5NBR*l95 90 70 50 - - - 100 - -CHC*25 10 30 50 3030 30 - 100 - - -CSM*3 - - - - 70 - ~ - - 100 CPE*4 - - - 70 - - - - 100 10SA*5 1 1 1 1 1 - 1 ZnO 5 5 5 5 - - - 5 ~
. MgO 5 5 5 5 10 10 - 5 5 10 10 C *6 50 5050 50 50 5050 50 50 50 50 50 Pla*7 15 1515 15 15 1515 15 15 15 15 15 1S VA*8 3.3 3.33.33.3 2 3 1 3.31 2 3 S *9 0.5 0.5 0.5 0.5 - -- - 0.5 - - - -~ _ _ .
PF*x 6.0 10.1 13.2 14.0 12.6 11.0 13.7 4.4 6.8 4.0 2.7 5.3 RF/IP RF RF RF RF RF RF RF IP IP IP IP IP
*1: NBR containing 32% by weight of AN (acrylonitrile) *2: epichloxohydrin-ethylene oxide-allyl glycidyl ether copolymer *3: CSM containing 35% by weight of CQ
*4: CPE containing 35% by ~eight of CQ
25 *5 stearic acid *6: FEF carbon *7: plasticizer *8: vulcanization accelerator *9: sulfur 30 *x: Pulling Force (kg/inch) *y: fracture of the rubber sheets of test pi.ece *z: peeling at the interface between the rubber sheets of test piece :, :
:
: .
' As 15 apparen~ from the test results shown in the TAEL~, all the test pleces formed of the compositions of Invention ~xample~ 1-7 were not peeled at the interface between the pair of superposed rubber sheets thereof, but fractured in the (sheet) rubber. That is, the rubber sheets themselves were fractured. Thi~ means high bonding strength at the interface between the rubber sheets of the tes~
pieces. 0~ the other hand, the test pieces formed of the compositions of Comparative Examples 1-5 were peeled at the interface between the pair of superpo~ed rubber sheets thereof. ~hi~ means low bonding strength at the interface~ a~ contrasted with the high bondiDg strength for Inve~tion E~ample~ 1-7. Thus, it is understood ~hat the compositions prepared according to the present invention (Invention ~xamples 1-7) are superior as materials for forming the inner layer of the inner rubber tube of rubber ho~es, to comparative compositions 1-5.
.
.
: . :.
, : . ., `, ' ' ' , :, ' . ,: :-.
Claims (6)
1. A rubber hose having:
an outer rubber tube and an inner rubber tube located radially inwardly of said outer rubber tube, said inner rubber tube comprising an inner layer and an outer layer located between said inner layer and said outer rubber tube, a reinforcing fiber layer disposed between said outer rubber tube and said outer layer of said inner rubber tube such that said inner and outer rubber tubes and said reinforcing fiber layer constitute an integral tubular body, said inner layer being formed of a first polymer blend of acrylic rubber and fluorine-containing resin, said acrylic rubber of said first polymer blend being a copolymer rubber produced by copolymerization of at least four monomers, said at least four monomers including at least one first monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate; at least one second monomer selected from the group consisting of substituted-alkyl esters of acrylic acid and methacrylic acid; at least one third monomer selected from the group consisting of diene, acrylate containing dihydrodicyclopentadienyl radical and methacrylate containing dihydrodicyclopentadienyl radical, ethylenically unsaturated compound containing epoxy radical, and ethylenically unsaturated compound containing active halogen, and at least one fourth monomer selected from the group consisting of other ethylenically unsaturated compounds capable of copolymerizing with said at least one first monomer, said at least one second monomer and said at least one third monomer, said outer layer being formed of a second polymer blend different from said first polymer blend, said second polymer blend containing epichlorobydrin rubber.
an outer rubber tube and an inner rubber tube located radially inwardly of said outer rubber tube, said inner rubber tube comprising an inner layer and an outer layer located between said inner layer and said outer rubber tube, a reinforcing fiber layer disposed between said outer rubber tube and said outer layer of said inner rubber tube such that said inner and outer rubber tubes and said reinforcing fiber layer constitute an integral tubular body, said inner layer being formed of a first polymer blend of acrylic rubber and fluorine-containing resin, said acrylic rubber of said first polymer blend being a copolymer rubber produced by copolymerization of at least four monomers, said at least four monomers including at least one first monomer selected from the group consisting of alkyl acrylate and alkyl methacrylate; at least one second monomer selected from the group consisting of substituted-alkyl esters of acrylic acid and methacrylic acid; at least one third monomer selected from the group consisting of diene, acrylate containing dihydrodicyclopentadienyl radical and methacrylate containing dihydrodicyclopentadienyl radical, ethylenically unsaturated compound containing epoxy radical, and ethylenically unsaturated compound containing active halogen, and at least one fourth monomer selected from the group consisting of other ethylenically unsaturated compounds capable of copolymerizing with said at least one first monomer, said at least one second monomer and said at least one third monomer, said outer layer being formed of a second polymer blend different from said first polymer blend, said second polymer blend containing epichlorobydrin rubber.
2. A rubber hose as set forth in claim 1, wherein said second polymer blend contains said epichlorohydrin rubber and at least one polymer selected from the group consisting of acrylonitrile-butadiene rubber, chlorosulfonated polyethylene, chlorinated polyethylene and acrylic rubber.
3. A rubber hose as set forth in claim 2, wherein said second polymer blend contains 1-50 parts by weight of said epichlorohydrin rubber per 100 parts by weight of the second polymer blend.
4. A rubber hose as set froth in claim 1, wherein said second polymer blend further contains at least one plasticizer, and acrylonitrile-butadiene rubber which contains, as a polymerization unit, 30-55% by weight of acrylonitrile, said polymer containing 15-80 party by weight of said at least one plasticizer per 100 parts by weight of said acrylonitrile-butadiene rubber.
5. A rubber hose as set forth in claim 1, wherein said acrylic rubber of said first polymer blend consists of, as polymerization units thereof, 30-80% by weight of said at least one first material, 20-70% by weight of said at least one second monomer, 0.1-10% by weight of said at least one third monomer and 1-30% by weight of said at least one fourth monomer.
6. A rubber hose as set forth in claim 1, wherein said fluorine-containing resin of said first polymer blend comprises polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluorethylene copolymer, polytetrafluoroethylene or ethylene-tetrafluoroethylene copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-319328 | 1987-12-16 | ||
| JP62319328A JPH01159245A (en) | 1987-12-16 | 1987-12-16 | Rubber hose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1316319C true CA1316319C (en) | 1993-04-20 |
Family
ID=18108959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000585832A Expired - Fee Related CA1316319C (en) | 1987-12-16 | 1988-12-14 | Rubber hose |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4942906A (en) |
| JP (1) | JPH01159245A (en) |
| CA (1) | CA1316319C (en) |
| DE (1) | DE3842284A1 (en) |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02190692A (en) * | 1989-01-18 | 1990-07-26 | Tokai Rubber Ind Ltd | Rubber hose |
| JPH0830544B2 (en) * | 1990-04-04 | 1996-03-27 | 豊田合成株式会社 | Multi-layer rubber hose |
| US5402831A (en) * | 1991-08-01 | 1995-04-04 | Asahi/America, Inc. | Restraint coupling assembly for double containment pipe system |
| WO1993009370A1 (en) * | 1991-11-05 | 1993-05-13 | Markel Corporation | Fuel system conduit and method of making same |
| FR2687619B1 (en) * | 1992-02-25 | 1994-04-08 | Elf Atochem Sa | TUBE FOR TRANSPORT OF FUEL. |
| JP2578705B2 (en) * | 1992-03-30 | 1997-02-05 | 東海ゴム工業株式会社 | Resin tube for fuel pipe and method of manufacturing the same |
| US6089277A (en) * | 1992-08-07 | 2000-07-18 | Tokai Rubber Industries, Ltd. | Fuel transporting hose having inner layer made of fluorine-contained resin |
| DE69431579T2 (en) * | 1993-08-03 | 2003-03-27 | Nitta Moore Co., Osaka | Fuel transport tube |
| JP2815306B2 (en) * | 1993-08-31 | 1998-10-27 | 株式会社ニチリン | Composite flexible hose |
| US5855976A (en) * | 1994-01-24 | 1999-01-05 | Nippon Zeon Co., Ltd. | Laminate of vulcanizable rubber composition layers, process for producing rubber laminate, and rubber laminate |
| JPH07299882A (en) * | 1994-04-28 | 1995-11-14 | Marugo Gomme Kogyo Kk | Hose end structure |
| DE9407360U1 (en) * | 1994-05-03 | 1994-07-07 | Polymelt Rolf Hansen GmbH, 86971 Peiting | Plastic pipe |
| US5447992A (en) * | 1994-06-13 | 1995-09-05 | The Goodyear Tire & Rubber Company | Heat and ozone resistant NBR/epichlorohydrin blends |
| US5588469A (en) * | 1994-10-17 | 1996-12-31 | Marugo Rubber Industries, Ltd. | Hose for automotive fuel piping |
| US5622210A (en) * | 1995-06-12 | 1997-04-22 | Lsp Products Group, Inc. | Flexible hose with composite core |
| DE19611311A1 (en) * | 1996-03-22 | 1997-09-25 | Dyneon Gmbh | Laminate |
| US5983923A (en) * | 1996-04-10 | 1999-11-16 | Lsp Products Group, Inc. | Water service box and connectors for PEX pipe |
| DE19635296A1 (en) * | 1996-08-30 | 1998-03-05 | Muendener Gummiwerk Gmbh | Fuel hose and process for its manufacture |
| US6161592A (en) * | 1998-03-31 | 2000-12-19 | Tokai Rubber Industries, Ltd. | Heat-resistant hose |
| US6306781B1 (en) | 1999-07-21 | 2001-10-23 | Senior Investments Ag | Expansion joint patch apparatus |
| DE10203123C1 (en) * | 2002-01-25 | 2003-02-06 | Sgl Acotec Gmbh | Compound pipe, to carry liquids and gases in chemical and other industries. has an outer layer of fiber reinforced plastics and an inner PTFE pipe layer, bonded together by an intermediate layer with a PFA surface |
| US20050287326A1 (en) * | 2004-06-29 | 2005-12-29 | Crane Resistoflex | Smooth inner bore hose with continuous fluoropolymer liner |
| US7553894B2 (en) * | 2005-07-28 | 2009-06-30 | 3M Innovative Properties Company | Cold-shrink article and method of making cold-shrink article |
| JP4936916B2 (en) * | 2006-02-01 | 2012-05-23 | 東海ゴム工業株式会社 | Heat resistant air hose for diesel |
| US7705085B2 (en) * | 2007-04-06 | 2010-04-27 | 3M Innovative Properties Company | Fluoroelastomer composition for cold shrink articles |
| US7642460B2 (en) * | 2007-04-06 | 2010-01-05 | 3M Innovative Properties Company | Cold shrinkable article including a fluoroelastomer composition |
| US20080280080A1 (en) * | 2007-05-07 | 2008-11-13 | Bandyopadhyay Pradip K | Cold shrinkable article including an epichlorohydrin composition |
| US8188178B2 (en) | 2007-05-07 | 2012-05-29 | 3M Innovative Properties Company | Cold shrinkable article including an epichlorohydrin composition |
| DE102007032149C5 (en) * | 2007-07-04 | 2016-03-10 | Elringklinger Ag | Elastomer sealing element and method for its production |
| US7973241B2 (en) | 2007-09-10 | 2011-07-05 | 3M Innovative Properties Company | Pressure restraining enclosure for cables |
| US7635813B2 (en) * | 2007-09-10 | 2009-12-22 | 3M Innovative Properties Company | Article and method for sealing fluid-containing cables |
| US8136845B2 (en) * | 2007-12-21 | 2012-03-20 | The Boeing Company | Clamp tension compensating, self-sustaining cuff apparatus and method |
| JP2012126015A (en) * | 2010-12-15 | 2012-07-05 | Daikin Industries Ltd | Laminate |
| DE102011052723A1 (en) * | 2011-08-16 | 2013-04-04 | Contitech Mgw Gmbh | Extruded molded article, in particular molded hose, with an embedded reinforcement of a fine knit and method for its production |
| CN105566883B (en) * | 2014-10-30 | 2019-12-17 | 株式会社捷太格特 | sealing material |
| RU177704U1 (en) * | 2017-05-25 | 2018-03-06 | Общество с ограниченной ответственностью "Промтехсервис" | HIGH-PRESSURE POLYMERIC REINFORCED PIPE |
| US20210008852A1 (en) * | 2018-03-14 | 2021-01-14 | Mitsui Chemicals, Inc. | Laminate and application of the same |
| CN112041356B (en) * | 2018-05-24 | 2022-06-10 | 优迈特株式会社 | Acrylic rubber and crosslinkable composition thereof |
| US11525546B2 (en) * | 2020-03-09 | 2022-12-13 | Chicago Gas Lines, Inc. | Pre-assembled gas plumbing system and methods |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5244889A (en) * | 1975-10-07 | 1977-04-08 | Bridgestone Corp | Thermostable rubber laminates |
| US4330017A (en) * | 1977-04-22 | 1982-05-18 | Nissan Motor Company, Limited | Rubber hose for automotive fuel line |
| USRE32230E (en) * | 1977-04-22 | 1986-08-26 | Nissan Motor Co., Ltd. | Rubber hose for automotive fuel line |
| JPS5930161B2 (en) * | 1980-06-16 | 1984-07-25 | 名糖産業株式会社 | Cationized dextran derivatives, their preparation and use |
| US4457799A (en) * | 1982-03-12 | 1984-07-03 | Polysar Limited | Bonding elastomers |
| JPS6033663A (en) * | 1983-08-03 | 1985-02-21 | Fujitsu Ltd | Analysis system of sentence structure |
| US4603712A (en) * | 1985-03-29 | 1986-08-05 | The Gates Rubber Company | Compounded polychloroprene formulation used as an adhesive layer in the manufacture of elastomeric articles |
| US4633912A (en) * | 1985-05-31 | 1987-01-06 | The Goodyear Tire & Rubber Company | Hose construction |
| US4685090A (en) * | 1985-11-27 | 1987-08-04 | Raychem Corporation | Tubular article |
| JPS62167991A (en) * | 1986-01-17 | 1987-07-24 | 豊田合成株式会社 | Hose |
| JPS62278395A (en) * | 1986-05-26 | 1987-12-03 | 東海ゴム工業株式会社 | Rubber hose |
| JPS6319486A (en) * | 1986-07-09 | 1988-01-27 | 東海ゴム工業株式会社 | hose |
| JPS63218348A (en) * | 1987-03-06 | 1988-09-12 | 東海ゴム工業株式会社 | Rubber hose |
-
1987
- 1987-12-16 JP JP62319328A patent/JPH01159245A/en active Granted
-
1988
- 1988-12-12 US US07/283,382 patent/US4942906A/en not_active Expired - Fee Related
- 1988-12-14 CA CA000585832A patent/CA1316319C/en not_active Expired - Fee Related
- 1988-12-15 DE DE3842284A patent/DE3842284A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0464507B2 (en) | 1992-10-15 |
| DE3842284A1 (en) | 1989-06-29 |
| JPH01159245A (en) | 1989-06-22 |
| US4942906A (en) | 1990-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1316319C (en) | Rubber hose | |
| CA1272540A (en) | Vulcanizable rubber compositions and applications thereof | |
| US8329274B2 (en) | Fuel hose | |
| US5937911A (en) | Fuel transporting hose having resin tube of fluorine-contained resin layer and other synthetic resin layer, and process of producing the resin tube | |
| US5362530A (en) | Gas-and-oil impermeable hose construction | |
| AU759941B2 (en) | Blends of fluoroelastomer interpolymers with thermo fluoroplastic interpolymers and the use of such blends in hoses | |
| US5427831A (en) | Fluoropolymer laminates | |
| AU687956B2 (en) | Multilayer article including a vulcanised elastomer directly combined with a thermoplastic | |
| US4603712A (en) | Compounded polychloroprene formulation used as an adhesive layer in the manufacture of elastomeric articles | |
| US5316046A (en) | Power steering hose | |
| EP0726293A1 (en) | Thermoplastic resin composition and laminate made therefrom | |
| AU749115B2 (en) | Air conditioning hose | |
| JP2005522639A (en) | Fuel refueling hose | |
| EP1348538B1 (en) | Heat resistant fuel hose | |
| WO1996000657A1 (en) | Composite fuel and vapor barrier tube and process for making same | |
| US6921565B2 (en) | Hose construction containing thermoplastic quadpolymers | |
| JPH0834886A (en) | Rubber composition, rubber-resin laminate and hose | |
| US5100734A (en) | Rubber laminate | |
| US5776570A (en) | Fuel hose and method of producing thereof | |
| US20050000582A1 (en) | Fuel hose | |
| JP3166382B2 (en) | Hose for automotive fuel piping | |
| EP0546564B1 (en) | Rubber laminates | |
| JPH01247158A (en) | Rubber hose | |
| JPS63218347A (en) | rubber hose | |
| JP2004149566A (en) | Hose for fuel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |